RU2043334C1 - 2-hydroxyethyltrialkylammonium 4-aminobenzoates and a method of their synthesis - Google Patents

Abstract

FIELD: organic chemistry. SUBSTANCE: product: 2-hydroxyethyltrialkylammonium 4-aminobenzoates of the general formula

where a) R₁=R₂=R₃ ethyl, empirical formula is C₁₅H₂₆N₂O₃, yield is 90% m. p. is 210-212 C; b) R₁=R₂=R₃=CH₃ R₁=R₂, yield is 85% m. p. is 220-222 C; c) R₃-methyl, R₁=R₂ butyl, yield is 100% Product is oil with refractory index 1.5152; d) R₃-methyl, R₁=R₂ - octyl, yield is 98% oil. Reagent 1: trialkylamine where (C₁-C₄)-alkyl, R₃ (C₁-C₈)-alkyl. Reagent 2: carbon dioxide. Reaction conditions: at 70-80 C in aqueous medium followed by successive addition of ethylene oxide and 4-aminobenzoic acid. Synthesized compounds were used in agriculture. EFFECT: improved method of synthesis. 3 cl, 2 tbl

Description

COO^-·R₁R₂R

CH₂CH₂OH где R₁=R₂=(С₁-С₄); R₃=(С₁-С₈) алкил. Заявляемые соединения относятся к солям четвертичных аммонийных оснований и до настоящего времени в литературе не описаны. Они могут найти применение в растениеводстве для повышения продуктивности сельскохозяйственных культур.The invention relates to biologically active substances of the General formula:
H ₂ N

COO ^- R ₁ R ₂ R

CH ₂ CH ₂ OH where R ₁ = R ₂ = (C ₁ -C ₄ ); R ₃ = (C ₁ -C ₈ ) alkyl. The inventive compounds belong to the salts of Quaternary ammonium bases and to date are not described in the literature. They can be used in crop production to increase crop productivity.

The closest analogues are trialkylammonium sulfonates, proposed to increase the yield of maize [1] Many quaternary ammonium salts are retordants and are of interest for use in agriculture to reduce plant height [2, 3]
The inventive compounds accelerate the growth and development of plants, increase their productivity and resistance to disease. So 4-aminobenzoate 2-hydroxyethyltriethylammonium when processing seed with a consumption rate of 30 g / t of seeds increased the yield of rice plants by 30% and ensured their resistance to pyriculariosis throughout the growing season.

 The method of obtaining the claimed compounds is based on the sequential interaction of tertiary amines with ethylene oxide in the presence of carbon dioxide, and then with 4-aminobenzoic acid.

 PRI me R 1. Obtaining 4-aminobenzoate 2-hydroxytetraethylammonium.

COO^-·(C₂H₅)

CH₂CH₂OH
(I)
В смесь из 140 мл триэтиламина, 160 мл воды при перемешивании и охлаждении (10-15^оС) барботируют двуокись углерода до образования прозрачного раствора, а затем в реакционную массу пропускают окись этилена до привеса 44 г (1 мол), поддерживая температуру в реакционной массе 70-80^оС. Затем к реакционной массе прибавляют 122,5 г (0,9 мол) 4-аминобензойной кислоты, нагревают при 50^оС до прекращения выделения двуокиси углерода 0,5 ч, охлаждают, отфильтровывают небольшой осадок 4-аминобензойной кислоты, фильтрат упаривают в вакууме и получают продукт 1. Выход 90% т.пл. (после промывки ацетоном) 210-212^оС.H ₂ N

COO ^- · (C ₂ H ₅ )

CH ₂ CH ₂ OH
(I)
To a mixture of 140 ml of triethylamine, 160 ml of water with stirring and cooling (10-15 ° ^C) bubbled with carbon dioxide to form a clear solution and then the reaction mass was passed to ethylene oxide weight gain of 44 g (1 mol), keeping the temperature in the reaction weight of 70-80 ° ^C. Then, thereto was added 122.5 g (0.9 mol) of 4-aminobenzoic acid was heated ^at 50 ° C until no more carbon dioxide for 0.5 hours, cooled, filtered slight precipitate of 4-aminobenzoic acid, the filtrate is evaporated in vacuum and get the product 1. Yield 90% so pl. (after washing with acetone) 210-212 ^about C.

 Found, C, 63.2; H, 9.38; N, 9.60.

C ₁₅ H ₂₆ N ₂ O ₃ .

 Calculated, C 63.6; H 9.59; N, 9.60.

COO^-·(CH₃)

CH₂CH₂OH
(II)
Выход 85% т.пл. 220-22^оС;
4-Аминобензоат 2-гидроксиэтилбутилдиметиламмония
H₂N

COO^-·C₄H₉(CH₃)

CH₂CH₂OH
(III)
Выход 100% масло n_D ²⁰=1,5152.In the conditions of example 1 receive:
4-aminobenzoate-2-hydroxyethyltrimethylammonium
H ₂ N

COO ^- · (CH ₃ )

CH ₂ CH ₂ OH
(Ii)
Yield 85% mp. 220-22 ^about C;
2-hydroxyethylbutyldimethylammonium 4-aminobenzoate
H ₂ N

COO ^- C ₄ H ₉ (CH ₃ )

CH ₂ CH ₂ OH
(III)
Yield 100% oil n _D ²⁰ = 1.5152.

CH₂CH₂OH
(IV)
Выход 98% масло.2-hydroxyethyl-octyldimethylammonium 4-aminobenzoate,
H ₂ N COO ^- C ₈ H ₁₇ (CH ₃ )

CH ₂ CH ₂ OH
(Iv)
Yield 98% oil.

 PRI me R 2. Determination of the effect of 4-aminobenzoates of 2-hydroxyethyltrialkylammonium on seed germination and development of seedlings of rice plants. Mutant 428 rice seeds were treated with substances I-IV by wet dressing with a consumption rate of 30 g / t of seeds in 10 l of water, then sown in flower pots and grown in a greenhouse under artificial light and full soil moisture capacity. The results are shown in table 1.

 PRI me R 3. Determination of the effect of compound I on the productivity of plants of rice varieties Mutant 3428 and their resistance to pyriculariosis. Rice seeds were treated by wet dressing with a 0.3% solution of substance 1 in water containing 0.2% sodium carboxymethyl cellulose (Na-CMC) with a flow rate of 10 l of solution per ton of seeds and sown in experimental plots (350 m) in 4 multiple repetition. The development of the disease was taken into account during the sweeping phase, and the yield was determined in the phase of complete ripeness of rice. The results are shown in table.2.

Claims (2)

1,4-Aminobenzoates of 2-hydroxyethyltrialkylammonium of the general formula

where R ₁ R ₂ C ₁ C ₄ -alkyl;
R ₃ C ₁ C ₈ -alkyl. 2. A method of obtaining 4-aminobenzoates of 2-hydroxyethyltrialkylammonium of the General formula

where R ₁ R ₂ C ₁ C ₄ -alkyl;
R ₃ C ₁ C ₈ -alkyl,
characterized in that the corresponding amine is treated with carbon dioxide, followed by sequential addition of ethylene oxide and 4-aminobenzoic acid.

Images